Alkylolamine salts of aliphatic acids and sulphonated fatty acids



Patented Apr. 7, 1931 proceed as fo ows:

UNITED STATES PATENT OFFICE JEAN GEORGES KERN AN D CHARLES J. BALL, 0] WILMINGTON, DELAWARE, 816K035 TO E. I. DU FONT DE NE'MO'URS DURATION OI DELAWARE ALKYLOLAMINE SALTS OF ALIPHATIO ACIDS AND Io Drawing.

This invention relates to alkylolamine salts of ali hatic acids both saturated and unsaturate and to the sulfonic acid derivatives of these acids and more particularly to the ethanolamine salts of the higher fatty acids.

This invention has as objects the preparation of soluble oils, solvents and detergents as well as of antiseptic soaps.

These objects are accomplished by making the salts of the bases known as alkylolamines or hydroxy-alkylamines, more particularl to the ethanolamines, by combination wit the fatty acids mentionedabove by any of the well known methods for the production of salts.

The bases used for our purpose ma be represented by the following general ormula:

Alb-OH where Alk represents an aliphatic or hy- ,droxy aliphatic radical, R and R represent hydrogen or an ali hatic radical or a hydroxy aliphatic radical or a poly hydroxy aliphatic radical. In making these new soluble oils we may proceedas follows:

The free fatty acids are combined directly with an organic base or a mixture of such bases. If the fatty acid is a solid the preparation is aided by the application of heat. It is also possible to start from the glycerides of the fatty acids, i. e., olive oil, cottonseed oil, castor oil, linseed oil and the like by saponifyinglthe glycerides by heating with the base to a igh temperature. I In this case we find that the reaction is complete when a sample of the mixture dissolves. entirely in watel'. If water is resent at the start this may be driven ofi, t e base not being volatile, until a concentrated product is left behind. When making these products by this method it is found that an excess of base is necessai y to give the most satisfactory results.

When pre aring the products obtained from the su honated fatty acids we may The acid product of the mixture of the sulphonated unsaturated acid as obtained by the & OOHIPANY, OI WILMINGTON, DELAWARE, A

SULPHONA'I'ED FATTY LOIDB Application filed August 4, 1927. Serial no. menu.

action of sulfuric acid on an unsaturated oil such as castor oil in the well known manner is freed of mineral acid by washing. It is then freed of water either by settling or by any other suitable means and then enough of the alkylolamine base is added at ordinary temperature to neutralize the acidity of the sulfonic acid group or of both sulfonic acid and the carboxylic acid groups. The following examples will serve to illustrate our method of procedure, but it is to be understood that the invention is not to be limited thereby:

E'wample 1 2828. 7 parts or tree oleic acid are mixed with 1490 parts of tri-ethanolamine.

Example 2 1960 parts of oleic acid are mixed with 950 parts of a mixture containing tri-ethanoiamine and 20% of di-ethanolamine.

The products resulting from this procedure are semi-solids, particularly water soluble and ready for use without further treatment. It is possible that the resultant material may be a compound of the base with the oleic acid but this has not been definitely established and is, in fact, immaterial to the success of the invention.

Example. 298. 5.1 parts 0! ricinoieic acid C H.(OH)CO0H are mixed with 105 parts di-ethanolamlne.

The resultant product is a clear yellow oil, very soluble in water.

Example 4 872 parts caster oil are mixed with 200 parts tri-ethanolamine 200 parts water. The above mixture is heated on the water bath for several hours. The saponification proceeds slowly and in order to make it complete within reasonable time it is of advanta e to add an excess for example 30% triet anolamine, above the quantity mentioned.

Ewarnpk 5 284. 89 parts of stearle acid are melted. Into the melt are H psi-ts tri-ethanolarina-atirring is continued at a mature 0! about C. until the mixture in The resultant roduct on cooling is a solid, not very solubl in water but very soluble in alcohol. It acts as an excellent assistant in promoting solution.

Example 6' 282 parts oleic acid 91 parts of amino-propane diol are heated together until completely mixed. The product is very soluble in alcohol. In water the solution is cloudy but becomes clear on the addition of some excess base, e. g. 15 to 20%.

Example 7 Ewample8 6 parts of a crude sulphonated oil made by the action of sulfuric acid on castor oil are mixed with 1 part of mono-etnanolamine.

Example 9 2. 7 parts of a crude suiphonated oil mixture in the form of free acids are m xed with 1 part ol 1 mixture dland trl-ethanolamlne.

The roducts of Examples 8 and 9 are entirely so uble in water. They are thick yellow oils resumably containing salts of the bases of t e sulfonic acids but this point has not been definitely established and is immaterial to the success of the invention. The products formed in this way are quite satisfactory for ordinary ur oses.

In dyeing onsol blue GD double paste, Schultz No. 842, on cotton yarn in the package machine, using of color, 2 sodium hydroxide, 3% hydrosulfite, the addition of 1% of the product formed by combining 1 mole of sulforecinoleic acid and 1 mole triethanolamine, containing di-ethanolamine, results in a brighter, more level dyeing.

The use in dyeing of the new compounds described in this case can be illustrated by 580- pafis thickening composed of starch or gums and a certhe following example:

Ewample 10 An 8.5%dyeing of Ponsol blue GD, Schultz No. 842, on 150 pounds of mercerized cotton piece goods is obtained as follows:

12.75 pounds Ponsol blue GD, Schultz No. 842, are mixed with 8.16 pounds of one of the compounds described in the examples of this case; 1 gallon of cold water is added and the suspension passed through a fine screen. A perfect speckless paste is thus obtained, which is added to the jigger dye bath composed of the following:

10 pounds caustic soda.

pounds hydroauiflte concentrated, 10 pounds being added immediately and 5 pounds being added after one passage of the goods.

100 gallons of water.

The temperature is raised to 110 F., and after complete reduction the dyeing started at this tem erature. The temperature is then allowe to rise during minutes to 125 C., and further dyed at this temperature for 10 to 15 minutes. Then give 1 wash, 4 passages in sodium perborate, 2 lbs. per 100 gals. at 120 F., 2 cold washes, 5 passes 1n boiling soap solution, 3 lbs. soap to 100 gallons, then rinse and wash in the open, dry and calender.

This example, illustrating the method of dyeing, is similar to Example 1 given in copending application Serial No. 210 715, filed by applicants on August 4, 1927. The difference between this example and the said Example 1 lies in the substitution of the novel.assistants herein disclosed by applicants.

Example 11 The new compounds described in this a plication may be used as assistants in the ma ng of vat color pastes in a manner similar to the pastes described in applicants patented application bearing Patent Number 1,705,118, granted March 19, 1929. The dyestufi' paste, as produced in the course of manufacture of Ponsol blue GD, Schultz No. 842, is converted into a press cake containing 30% of dry color. 400 parts of the press cake are then mixed with 20 parts of glycerine and 580 parts of one of the assistants repared according to Examples 1 to 9 and xample 13 of this application. It is possible to vary the quantities considerably without losing the advantages of this invention.

Example 12 The new compounds described in this case may be used in printing pastes containing lakes of basic colors. The mode of rocedure in usin such a printing paste is i lustrated in the ollowing examp e:

10 parts basic color (suitable for discharge printing) 50 parts givcerine 50 parts of any one of the products described in Examples 1 to 9 and Example 18 of this application 250 parts water in amount of sodium hydrosuiflte-tormaldehyde necessary to cut the ground 60 purge iiapnin dissolved in equal parts 01 water or a co 0.

The textile or other material printed one or more hydro prise part of applicants herein disclosed invention.

Example 18 If a pure product is needed the operation may be carried out as follows:

In the above case the addition of a further molecular equivalent of base produces a more soluble oil. The reason may be that the extra quantity of base combines with the carboxyl group but again this point has not been determined. 7

In the above examples any one of the bases as defined by the general formula given above may be used either alone or in mixture. The fatty acids may also be varied through a wide range.

By the term alkylol, as used herein, we mean to include an alkyl radical in which us are replaced by a hydroxyl group, an may be represented by the' following:

We have found that these products, which are essentiall organic soaps possess a property of soaps without the high alkalinity .'characteristic of sodium or potassium salts of the fatty acids. These products for these reasons have a distinct advantage for many purposes and particularly as assistants in dyeing, and those compounds which are derived from sulphonated castor oil by the process mentioned are in many ways superior to ordinary sulphonated oils. Their superiority is evidenced by the greater evenness of the shades developed the better utilization of the color and the greater brilliance of the dyeing.

When added to water they bring about solution or dispersion in so fine a form as to appear a solution of insoluble organic bases such as amino-azo-benzene, para-nitro-benzene, azo-diphenylamine, benzene-azo-naphthalene-azo phenol, Rosanthrene base, di-ethyl-para-amido-phenol- 1 :4 naphtho-quinone-mono-imide, 2.4. dinitro-benzene-l-azo-di-ethyl-aniline, etc. It takes about 2 to 5 parts of the solvent for 1 part of the insoluble base. Them solutions may be used very successfully for the purpose (if dyeing fibers of esterified cellulose.

It has also been found that these soaps dissolve metallic hydroxides and oxides, for example, mercuric oxide, and this property indlcates their probable value in pharmacology, for example, in the production of antiseptic soaps and the like.

As many apparently widely difierent emwith said bodiments of this invention may be made without departing from the s irit thereof, it is to be understood that we 0 not intend to limit ourselves to the specific embodiments thereof except as indicated in the appended claims.

We claim 1. In a process of applyinga dye to textile fibres, the step which comprises mixing with said dye a product resulting from saponifying a higher fatty acid and glyceride with an alkylolamine.

2. In a process of applying a dye to textile fibres, the step which comprises mixing with said dye a product resulting from the saponification of castor oil with an excess of tri-ethanolamine.

3. In a process of applying a dye to textile fibres the step which comprises mixing with said, dye an alkylolamine salt of a higher fatty acid.

4. In a process of applying a dye to textile fibres, the step which comprises mixing dye an ethanolamine salt of a higher fatty acid.

5. In a process of applying a dye to textile fibres, the step which comprises mixing with said dye the product resulting from combining an alkylolamlne with an acid taken from a group consisting of oleic, ricinoleic and stearic.

6. In a process of applying a dye to textile fibres, the step which comprises mixing with said dye the product resulting from combining with tri-ethanolarnine an acid taken from a group consisting of oleic, ricinoleic and stearic.

7. In a process of applying a dye to textile fibres, the step which comprises mixing with said (1 e a product resulting from combining wit a mixture of di-ethanolamine and tri-ethanolamine an acid taken from a group consisting of oleic, ricinoleic and steam]; f 1 d 8. a process 0 a p yin a e to textile fibres, the step which col npriszs mixing with said dye a product resulting from saponifying a vegetable oil with an alkylolamine.

9. In a process of applying a dye to textile fibres, the step which comprises mixing w th said dye a product resulting from combin ng a higher fatty acid and tri-ethanolamine.

10. In a process of appl in a d e to textile fibres, the step which coi pris s mixing with said dye a product resulting from combining a higher fatty acid and a compound having the following formula:

4 Alli-O H N\ 1 1 represent a. monovalent substance from the group consisting of hydrogen, aliphatic radicals, hydroxy aliphatic radicals and polyhydroxy aliphatic radicals.

11. In a process of applying a dye to textile fibres, the step which comprises mixing with said dye a product resulting from combining a higher fatty acid and a di-ethanolamine.

12. In a process of applying a dye to textile fibres, the step which comprises mixing with said dye a roduct resulting from combining a higher atty acid and mono-ethanolamine.

13. In a process of applying a dye to textile fibres, the step which comprises mixing with said dye a product resulting from combining a higher fatty acid and a mixture of diand tri-ethanolamine.

14. In a process of ap lying a dye to textile fibres, the step whic comprises mixing with said dye a product resulting from combining a higher fatty acid and at least one of the oup consistin of mono-ethanolamine, di-e i a'nolamine an tri-ethanolamine.

In testimony whereof we afiix our signatures.

JEAN GEORGES KERN.

CHARLES J. SALA.

represent a. monovalent substance from the roup consisting of hydrogen, aliphatic radicals, hydroxy aliphatic radicals and polyhydroxy aliphatic radicals.

11. In a process of applying a dye to textile fibres, the step which comprises mixing with said dye a product resulting from combining a higher fatty acid and a di-ethanolamine.

12. In a process of applying a dye to textile fibres, the step which comprises mixing with said dye a roduct resulting from com bining a higher atty acid and mono-ethanolamine.

13. In a process of applying a dye to textile fibres, the step which comprises mixing with said dye a product resulting from combining a higher fatty acid and a mixture of diand tri-ethanolamine.

14. In a process of ap lying a dye to textile fibres, the step Wh1c comprises mixing with said dye a roduct resulting from combining a higher atty acid and at least one of the group consistin of mono-ethanolamine, di-ethanolamine an tri-ethanolamine.

t In testimony whereof we aflix our signaures.

JEAN GEORGES KERN.

CHARLES J. SALA.

Certificate of Correction Patent No. 1,799,821. Granted April 7, 1931, to

JEAN GEORGES KERN ET AL.

It is hereby certified that error appears in the rinted s 'fic l i t i tl numbered patent requiring correction as follows Pa 1, li fx e s ij r the di' zn dl a 8153311 55,?) read Ct',,H t,kSOH) UOOH; n that the said Letters Patent 4 W1 l8 corr c of the case in the Patent 050: ion ereln that the same may conform to the ['92 m d Signed and sealed this 12th day of May, A. D. 1981.

M. J. MOORE, Acting Oonwniuionu of Patents.

Certificate of Correction Granted April 7, 1931, to

JEAN GEORGES KERN in AL.

It is hereby certified that error appears in the printed specification of time abovenumbered patent requiring correc'tion as follows: Pa 1, line 81, for the fo mula C H,,(OH)COOH read C H AOH) COOH; an that the said Letters Patent, should be read with this correction therein that the same may conform to the reuord of the case in the Patent Ofice.

Signed and sealed tms 12th day of May, A. D. 1981.

Patent No. 1,7 99,821.

[sun] M. J. MOORE, Aoting Commissioner of Patents. 

